4-halo-2,4-diolefinic fatty acids and esters

ABSTRACT

Novel unsaturated aliphatic carboxylic esters substituted at C-4 with a halogen atom, intermediates therefor, and the control of insects.

United States Patent Henrick Jan. 28, 1975 4-HALO-2,4-DIOLEFINIC FATTY ACIDS [56] References Cited AND ESTERS UNITED STATES PATENTS Inventor: Clive Henrick. Palo Alto. Calif 3,l93,565 7/1965 Tschesche et ul. 260/408 [73] Assign: Zolcon Corporation, Pal) Alto 3.793353 2/1974 Henrick i. 260/405 Calif. Primary IiraminuF-Altun D. Rollins [22] Flled: 1974 Assistant Examiner-Diana G. Rivers 211 App] 431 521 Attorney. Agent, or FirmDonaldl W. Erickson;

Lee-Louise H. Priest Related U.S. Application Data [62] Division of Ser. No. 252,383. May l 1, I972, Pat. No.

1821264 [57] ABSTRACT Novel unsaturated aliphatic carboxylic esters substi [52] U.S. Cl. 260/408, 260/DlG. 44 tuted at C-4 with a halogen atom, intermediates there- [51] Int. Cl C07c 69/62, AOln 9/24 for, and the control of insects. [58] Field of Search 260/DIG. 44, 408

16 Claims, N0 Drawings 4-llIALO-2,4-DIOLEFINIC FATTY ACIDS AND ESTERS This is a division of Ser. No. 252,383, filed May ll,

1972, now US. Pat. No. 3,821,264.

This invention relates to new unsaturated aliphatic carboxylic esters substituted at C-4 with a halogen atom, synthesis thereof, intermediates therefor, and the control of insects. More particularly, the new carboxylic esters of the present invention are represented by the following formula (A):

n 2 R R o 4 l l l n l l R -p-|c-(ca -cn-(cn -cn=T-c=cn- -OR (A) Z Z X wherein,

m is zero, one or two;

n is one, two or three;

X is a halogen atom;

R is hydrogen, lower alkyl, cycloalkyl, aryl or aralkyl;

each of R, R R and R is lower alkyl;

R is hydrogen or methyl;

Z is hydrogen, lower alkyl, halogen atom, hydroxy,

lower alkoxy or lower acyloxy; and

Z is hydrogen or. together in Z, a carbon-carbon bond.

The compounds of formula A are useful for the control of insects. The utility of these compounds as insect control agents is believed to be attributable to their juvenile hormone activity. They are preferably applied to the immature insect, namely, during the embryo, larvae or pupae stages in view of their effect on metamorphosis and otherwise causing abnormal development leading to death or to inability to reproduce. These compounds are effective control agents for Heteropterans, such as Lygaeidae, Miridae and Pyrrhocoridae; Homopterans, such as Aphididae, Coccidae and .lassidae;' Lepidopterans, such as Pyralidae, Noctuidae and Gelechiidae; Coleopterans, such as Tenebrionidae, Crysomelidae and Dermestidae; Dipterans, such as Culicidae, Muscidae and Sarcophagidae; and other insects. The compounds can be applied at low dosage levels of the order of 0.0] ug. to l pg. per insect. Suitable carrier substances include liquid or solid inert carricrs, such as water, acetone, xylene, mineral or vegetable oils, talc, vermiculite, natural and synthetic resins and silica. Treatment of insects in accordance with the present invention can be accomplished by spraying, dusting or otherwise contacting the insect, directly or indirectly, with one or more compounds of formula A. Generally, a concentration of less than 25% of the active compound is employed. The formulations can include insect attractants, emulsifying agents or wetting agents to assist in the application and effectiveness of the active ingredient.

In the description hereinafter, each of R-R X, Z and Z is as defined above, unless otherwise specified.

In one embodiment of the present invention, the compounds of formula A, wherein Z is hydrogen, are synthesized according to the following outlined In the practice of the above outlined synthesis, a 2,4- diunsaturated ester of formula I is reacted with a peracid, such as m-chloroperbenzoic acid or perphthalic acid in an organic solvent to form the 4,5-epoxide of formula ll. The 4,5-epoxide is converted into the halohydrin (III) by treatment with the appropriate hydrogen halide in an organic solvent. The halohydrin (lll) is then converted into the corresponding S-mesylate by treatment with methanesulfonyl chloride, which is treated with 1,5-diazobicyclo[5.4.0]undec-5-ene to prepare the 4-halo-2,4-diunsaturated ester of formula A (R' represents lower alkyl, cycloalkyl, aralkyl or aryl).

In another embodiment of the present invention. 4-halo-2,4-diunsaturated compounds and 4-halotriunsaturated compounds (2' together with Z is a carhon-carbon bond) of formula A are prepared by the reaction of a phosphonate of formula IV with an a aldehyde of formula V. This reaction is conducted in the presence of a base, such as sodium hydride, in an organic solvent (R" is lower alkyl).

In another embodiment of the present invention, compounds of formula A are prepared by ylid reaction using an ylid offormula VI in reaction with an aldehyde of formula V. The ylid (Vl) can be prepared using the procedure of Ma'rkl, Chem. Ber. 94, 2996 (1961) and ibid., 95, 3003 (1962) starting with an ylid of formula VII. R represents aryl, aralkyl or cycloalkyl.

Acids of formula A (R is hydrogen) can be prepared by hydrolysis with base, such as potassium carbonate in an organic solvent, such as a lower alcohol. Other esters of formula A can be prepared by conversion of the acid into the acid halide as by treatment with oxalyl chloride, or the like, and then reaction of the acid halide with the alcohol corresponding to the ester moiety desired.

The tri-unsaturated esters of formula A (2 together with Z is a carbon-carbon bond) also serve as precursors for compounds of formula A wherein Z is hydrogen and Z is halogen atom, hydroxy, alkoxy, or acyloxy. Compounds of formula A wherein Z is halogen atom can be prepared by treatment of the tri-unsaturated precursor (A) with hydrogen halide in an organic solvent. Compounds of formula A wherein Z is hydroxy can be prepared from the tri-unsaturated precursor by the addition of water to the terminal olefinic bond using a mercuric salt followed by reduction using a borohydride, hydrazine or sodium amalgam. By conducting this reaction in the presence of an alcohol, such as methanol, ethanol isopropanol, t'butanol, and the like, the corresponding ether (Z is alkoxy) is prepared. See Brown and Rei, J. Am. Chem. Soc. 91, 5646 (1969) and Wakabayashi, J. Med. Chem. 12, 191 (January, 1969). Compounds of formula A wherein Z is acyloxy can be prepared from the hydroxy precursor (A, Z is hydroxy) by reaction with a carboxylic acid chloride or anhydride.

The di-unsaturated esters of formula 1 and the aldehydes of formula V can be prepared as described in application Ser. No. 187,897 and Ser. No. 187,898, each filed Oct. 8, 1971, now U.S. Pat. Nos. 3,755,411 and 3,752,843, respectively. the disclosures of which are incorporated by reference.

The term lower alkyl, as used herein, refers to a straight or branched chain saturated aliphatic hydrocarbon group having a chain length of one to six carbon atoms, e.g., methyl, ethyl, propyl, i-propyl, n-butyl, sbutyl, t-butyl, pentyl and hexyl.

The term cycloalkyl, as used herein, refers to a cyclic alkyl group containing three to eight carbon atoms, e.g., cyclopropyl, cyclopentyl and cyclohexyl.

The term aralkyl, as used herein, refers to a monovalent hydrocarbon group in which a hydrogen atom of a lower alkyl group is substituted by an aryl group, such as benzyl, phenethyl, methylbenzyl, naphthylmethyl and naphthylethyl containing from seven to twelve carbon atoms.

The term lower acyloxy, as used herein, refers to an aliphatic hydrocarbon carboxylic acyloxy group of one to six carbon atoms.

The presence of an olefinic bond at position C-2 and C-4 of the compounds of formula A give rise to four isomers, each of which is embraced by the present invention. The presence of three olefinic bonds in compounds of formula A give rise to eight isomers, each of which is embraced by the present invention. As mentioned above, a mixture of isomers is suitably employed for the control of insects, such as a mixture containing the trans(2), trans(4) isomer and the cis(2), trans(4) isomer. The conditions of the syntheses described herein and the reactants can be selected so as to favor formation of one isomer, such as the all trans isomer, over the formation of other isomers. The selection of appropriate conditions and reactants to favor formation of one isomer over another will be apparent to those of ordinary skill in the art giving due consideration to the specific examples hereinafter. 1n the specific examples hereinafter, when isomerism is not specified, it is understood to include a mixture of isomers which, if desired. can be separated using known separation methods.

The following examples are provided to illustrate the practice ofthe present invention. Temperature is given in Centigrade.

The term halogen atom". as used herein, refers to bromo. chloro, fluoro and iodo.

EXAMPLE 1 To 15 g. of ethyl 3.7.11-trimethyldodeca-2 4- dienoate in ml. of methylene chloride is slowly added 12.6 g. of 85% m-chloroperbenzoic acid in ml. of methylene chloride with stirring and maintaining temperature at about 25". After addition is complete, the reaction mixture is left at room temperature for 4 days. Sodium bicarbonate (5%) is added and the mixture extracted with ether. The organic phase is washed with 5% sodium bicarbonate, water and brine, dried over calcium sulfate and solvent removed under re duced pressure to yield ethyl 4,5-oxido-3,7,11- trimethyldodec-Z-enoate, which can be purified by thin-layer chromatography eluting with ether/hexane Following the process of this example, ethyl 4,5- oxido-l l-methoxy-3,7,l l-trimethyldodec-2-enoate is prepared from ethyl ll-methoxy-3,7,1l-trimethyldodeca-2,4-dienoate.

EXAMPLE 2 To 1.4 m1. of concentrated hydrochloric acid (37%) is added 2 g. of ethyl 4,5-oxido3,7,l l-trimethyldodec- 2-enoate in 20 ml. of anhydrous ether, with stirring, below 5. Stirring is continued for 3 hours. Excess HCl is neutralized with solid sodium carbonate. The aqueous layer is saturated with ammonium sulfate, separated and extracted with ether. The ether solutions are combined, washed with 5% ammonium sulfate, dried over sodium sulfate and concentrated. The concentrate is diluted with ether and chromatographed on one meter plates eluting with ether/hexane (US) to give ethyl 4-chloro-5-hydroxy-3,7,1 l-trimethyldodec-Z- enoate.

By use of the above process, ethyl 1l-methoxy-4- chloro-5-hydroxy-3,7,1 l-trimethyldodec-2-enoate is prepared from ethyl 1l-methoxy-4,5-oxido-3,7,1 1- trimethyldodec-Z-enoate.

EXAMPLE 3 Methanesulfonyl chloride (0.43 ml.) is added to a solution of 0.9 g. of ethyl 4-chloro-5-hydroxy-3.7,l1- trimethyldodec-2-enoate and 0.43 g. of triethylamine in 30 ml. of methylene chloride at 0. The reaction mixture is stirred for 1 hour. The mixture is diluted with methylene chloride, washed with ice water, 10% HCl solution, saturated sodium bicarbonate solution and brine, dried over calcium sulfate and solvent evaporated under reduced pressure to yield ethyl 4-chloro-5- methanesulfonyloxy-3,7,1 1-trimethyldodec-2-enoate, which can be purified by thin-layer chromatography.

In the same way, ethyl 4-chloro-5- methanesulfonyloxy-l 1-methoxy-3,7,l l-trimethyldodec-Z-enoate is prepared from ethyl 4-chloro-5- hydroxy-l l-methoxy-3,7,l l -trimethyldotlcc-Z-enoatc.

EXAMPLE 4 A mixture of 0.87 g. of ethyl 4-chloro-5- methanesulfonyloxy-3,7,l 1-trimethyldodec-2-enoate,

0.34 g. of l,5-diazobicyclo[5.4.0]undec-5-ene and 30 ml. of dimethylformamide is stirred, under nitrogen, at room temperature for 3 hours. The mixture is diluted with ether, washed with HCl, saturated sodium bicarbonate solution, water and brine, dried over calcium sulfate and solvent removed under reduced pressure to give ethyl 4-chloro-3,7,l l-trimethyldodeca-2,4- dienoate, which can be purified by thin-layer chromatography eluting with ether/hexane (1/5).

Ethyl 4-chloro-l 1-methoxy-3,7,1 l-trimethyldodeca- 2,4-dienoate is prepared from ethyl 4-chloro-5- methanesulfonyloxy-l 1-methoxy-3,7,1 l-trimethyldodecusing the process of this example.

EXAMPLE 5 Diethyl 3-ethoxycarbonyl-2-methylprop-Z-enyl phosphonate (0.1 mole) is added dropwise, at to a slurry of 0.1 mole of Nal-l in 400 ml. of tetrahydrofuran. The mixture is stirred about 1 hour or until hydrogen evolution ceases. Then 0.1 mole of bromine is added dropwise to the mixture, with stirring, while cooling in a cooling bath (0 to 20). At about 0, additional Nal-l (0.1 mole) is added and stirred until evolution of hydrogen ceases. Then 0.1 mole of 3,7-dimethyloct--en-l-al is added dropwise and left overnight at room temperature. The reaction mixture is worked up by washing with water, extracting with ether, drying over calcium sulfate, and evaporation of solvent under redueed pressure to give ethyl 4-bromo3,7,l ltrimethyldodeca-2,4,IO-trienoate, which can be purifled by chromatography, if desired.

By repeating the process of this example using chlorine in place of bromine, there is prepared ethyl 4- chloro-3 ,7, 1 1-trimethyldodeca-2,4, 1 O-trienoate.

EXAMPLE 6 Following the procedure of Example 1, each of the esters under Column l is epoxidized to prepare the respective 4,5-epoxide under Column ll:

isopropyl 3,7,1 l-trimethyldodeca-2,4-dienoate, ethyl 3,7,10,1 1,-tetramethy1dodeca-2,4-dienoate, ethyl 3,7,1 1-trimethyltrideca-2,4-dienoate,

ethyl 3,7,lO-trimethylundeca-Z,4-dienoate, ethyl 3 ,7, l O-trimethyldodeca-Z ,4-dienoate,

isopropyl l 1-methoxy-3,7,l 1-trimethyldodeca-2,4-

dienoate,

isopropyl l l-methoxy-3,7,l l-trimethyltrideca-2,4-

dienoate,

ethyl 1 1-methoxy-3,7,l0,1 l-tetramethyldodeca-2,4-

dienoate,

ethyl l 1-chloro-3,7,1 l-trimethyldodeca-2,4-

dienoate,

ethyl lO-methoxy-3,7,10-trimethylundeca-2,4-

dienoate,

ethyl l l-acetoxy-3,7,1 1-trimethyldodeca-2,4-

dienoate,

ethyl 3,1 l-dimethyl-7-ethyltrideca-2,4-dienoate.

isopropyl 4,5-oxido-3,7,l l-trimethyldodec-2-enoate,

ethyl 4,5-oxido-3,7, l 0,1 1-tetramethyldodec-2- enoate,

ethyl 4,5-oxido-3,7,1 l-trimethyltridec-Z-enoate,

ethyl 4,5-oxido-3,7,lO-trimethylundec-Z-enoate,

ethyl 4,5-oxido-3,7,lO-trimethyldodec-2-enoate,

isopropyl 4,5-oxido-l 1-methoxy-3,7,l l-trimethyldodcoZcnoate,

isopropyl 4,5-oxido-1 1-methoxy-3,7,l l-trimethyltridec-Z-enoate,

ethyl 4,5-oxido-1 1-methoxy-3,7,10,l 1-

tetramethyldodec-Z-enoate,

ethyl 4,5-oxido-1 l-chloro-3,7,1 l-trimethyldodec-Z- enoate,

ethyl 4,5-oxido-lO-methoxy-3,7,lO-trimethylundec- Z-enoate,

ethyl 4,5-oxido-1 1-acetoxy-3,7,1 l-trimethyldodec-Z- enoate,

ethyl 4,5-oxido-3,1 l-dimethyl-7ethyltridec-2-enoate.

EXAM PLE 7 Using the process of Example 2, each of the epoxides under Column ll is converted into the respective chlorohydrin under Column lll:

Ill isopropyl 4-chloro-5-hydroxy-3,7,l l-trimethyldodec-Z-enoate, ethyl 4-chloro-5hydroxy-3,7,10,1 l-tetramethyldodec-2enoate,

ethyl 4-chloro-5-hydroxy-3,7,ll-trimethyltridec-2- enoate, ethyl 4-chloro-5-hydroxy-3,7,10-trimethylundec-2' enoate, ethyl 4-chloro-5-hydroxy-3,7,l0-trimethyldodec-2- enoate, isopropyl 4-chloro-5-hydroxy-l1-methoxy-3,7,l l-

trimethyldodec-Z-enoate,

isopropyl 4-chloro-5-hydroxy-l l-methoxy-3,7,1 1-

trimethyltridec-2-enoate,

ethyl 4-chloro-5-hydroxy-1 l-methoxy-3,7, l 0,1 1-

tetramethyldodec-2-enoate,

ethyl 4-chloro-5-hydroxy-1 1-chloro-3,7,1 1-

trimethyldodec-Z-enoate,

ethyl 4-chloro-5-hydroxy-10-meth0xy-3 ,7 l 0- trimethylundec-Z-enoate,

ethyl 4-chloro-5-hydroxy-1 1-acetoxy-3,7,1 l-

trimethyldodec-2-enoate,

ethyl 4-chloro-5-hydroxy-3,l1-dimethyl-7-ethyltridec-Z-enoate.

By use of the process of Example 3, each of the chlorohydrins under Column 111 is converted into the respective 5-mesylate, which is used in the process of Example 4 to prepare the respective 4-chloro-2,4-diunsaturated compound under Column lV.

isopropyl 4-chloro-3,7,l l-trimethyldodeca2,4-

dienoate, ethyl 4-chloro-3 ,7 l 0,1 l-tetramethyldodeca-2,4-

dienoate,

ethyl 4-chloro-3,7,l l-trimethyltrideca-2,4-dienoate,

ethyl 4-chloro-3,7, l O-trimethylundeca-2,4-dienoate,

ethyl 4-chloro-3,7,lO-trimethyldodeca-Z,4-dienoate,

isopropyl 4-chloro-l l-metho xy-3 ,7,1 l-trimethyldodeca-2,4-dienoate,

isopropyl 4-chloro-l 1-metho xy-3,7,1 l trimethyltrideca-2,4-dienoate,

ethyl 4-chloro-1 l-methoxy-3 ,7,1 0,1 1 -tetramethyldodeca-2,4-dienoate,

ethyl 4,1 l-dichloro-3,7,1 l-t:rimethyldodeca-2,4-

dienoate,

ethyl 4-chloro-l0-methoxy-3,7,l0-trimethylundeca 2,4-dienoate,

ethyl 4-chloro-l l-acetoxy-3,7,l l-trimethyldodeca- 2,4-dienoate,

ethyl 4-chloro-3,1 l-dimethyl-7-ethyltrideca-2,4

dienoatc.

EXAMPLE 8 The process of Example is repeated using each of 3,7-dimethylnon 6-en-l-al, 3,7-dimethyloctan-l-al, 3,7,7-trimethyloctan-l-al, 7-hydroxy-3,7- dimethyloctan-l-al, 3,6-dimethylhept-5-en-l-al, 3 ,6,7-trimethyloct-6-en- 1 -al, 6-hydroxy-3 ,6-dimethylheptan-l-al and 7-hydroxy-3,6,7-trimethyloctan-l-al as the aldehyde reactant in place of 3,7-dimethyloct-6-enl-al to prepare the respective 4-bromo-2,4-diunsaturated ester under Column V.

ethyl 4-bromo-3,7,l 1-trimethyltrideca-2,4,

trienoate,

ethyl 4-bromo-3,7,l l-trimethyldodeca-2,4-dienoate,

ethyl 4-bromo-3,7,l 1,1 l-tetramethyldodeca-ZA- dienoate,

ethyl 4-bromo-l l-hydroxy-3,7,l l-trimethyldodeca- 2,4-dienoate,

ethyl 4-bromo-3 ,7, l O-trimethylundeca-2,4,9-

trienoate,

ethyl 4-bromo-3,7,l0,l1-tetramethyldodeca-2,4,l0-

trienoate,

ethyl 4-bromo-10-hydroxy-3,7,lO-trimethylundeca- 2,4-dienoate, ethyl 4-bromo-l l-hydroxy-3,7.l0,l l-tetramethyldodeca-2,4-dienoate. In the same way, the 4-chloro derivatives otherwise corresponding to the esters under Column V can be prepared.

EXAMPLE 9 EXAMPLE 10 A mixture of 3.0 g. of sodium acetate and ml. of acetic anhydride is stirred at room temperature for 0.5 hour. To the mixture is added 2.7 g. of ethyl 4-chloro- 1 l-hydroxy-3,7,l l-trimethyldodeca-2,4dienoate. The mixture is warmed up to about 80 and left for about 16 hours. After cooling, the mixture is poured into saturated sodium bicarbonate and extracted with ether.

The combined ether extracts are washed with aqueous sodium bicarbonate, water and saturated sodium chloride solution, dried over calcium sulfate and evaporated under reduced pressure to yield ethyl 4-chloro- 1 1-acetoxy-3,7,1 l-trimethyldodeca-2,4-dienoate.

EXAMPLE 1 1 To a solution of 2.0 g. of ethyl 4-chloro-3,7,lltrimethyldodeca-2,4,lO-trienoate in ml. of ethanol, cooled in an ice bath, is slowly added 5.2 g. of acetyl chloride. The reaction mixture is allowed to rise to room temperature and then stirred for about 60 hours. The mixture is concentrated under reduced pressure and then poured into water/hexane. The organic layer is separated, washed with aqueous sodium bicarbonate,

water and brine, dried over calcium sulfate and solvent removed to yield ethyl 4,1 l-dichloro-3,7,l l-trimethyldodeca-2,4-dienoate.

EXAMPLE 12 To 0.5 g. of 4-chloro-1l-methoxy-3,7,ll-trimethyldodeca-2,4-dienoic acid in 10 ml. of benzene. under nitrogen. is added 0.17 ml. of oxalyl chloride. The mixture is stirred for about one hour and then allowed to stand 1.5 hours. Two ml. of isobutanol is added. After 3 hours, ether is added. The mixture is washed with aqueous sodium bicarbonate, water and brine, dried over calcium sulfate and concentrated under reduced pressure to yield isobutyl 4-chloro-l l-methoxy-3,7,l ltrimethyldodeca-2,4-dienoate.

Using each of t-butanol, cyclopentanol, benzyl alcohol, phenol, s-butanol and methanol in the above process, there is prepared:

t-butyl 4-chloro-l l-methoxy-3,7,1 l-trimethyldodeca-2,4-dienoate,

cyclopentyl 4-chloro-l l-methoxy-3,7,1 l-trimethyldodeca-2,4-dienoate,

benzyl 4-chloro-1 l-methoxy-3 ,7 ,1 l-trimethyldodeca-2,4-dienoate,

phenyl 4-chloro-1 1-methoxy 3,7,l l-trimethyldodeca-2,4-dienoate,

s-butyl 4-chloro-l l-methoxy-3,7,l l-trimethyldodeca-2,4-dienoate,

methyl 4-chloro-l l-methoxy-3,7,l l-trimethyldodeca-2.4dienoate.

EXAMPLE 13 To an ice cold solution of 2.0 g. of isopropyl 4- chloro-3,7,l l-trimethyldodeca-2,4, l O-trienoate in ml. of isopropanol is added 2.29 g. of mercuric acetate over about 15 minutes. The mixture is stirred at ice temperature for three hours and then at room temperature for about 17 hours. A solution of 1.21 g. of potassium hydroxide, 5 ml. of water, and 20 ml. of isopropanol is then added to the mixture cooled in an ice bath. Then 0.126 g. of sodium borohydride is added in small portions and stirring continued for 1 hour. The mixture is then stirred with Celite and mercury filtered off. The filtrate is concentrated under reduced pressure, diluted with water and extracted with ether. The combined ether extracts are washed with water and brine, dried over calcium sulfate and solvent removed to yield isopropyl 4-chloro-l l-isopropoxy-3,7,l l-trimethyldodeca-2,4-dienoate.

EXAMPLE 14 A solution of 0.1 mole of triphenylphosphine 3- ethoxycarbonyl- 1-chloro-2-methylprop-2-ene (prepared from triphenylphosphine-3-ethoxycarbonyl-2- methylprop-2-ene using phenyl iodide chloride in triethylamine by the method of Markl, supra) and 0.1 mole of 3,7-dimethyloct-6-en-l-al in toluene, under nitrogen, is refluxed about 6 hours. Toluene is removed under reduced pressure, pentane added and they mixture filtered. The filtrate (combined with pentane washings) is evaporated under reduced pressure to yield ethyl 4-chloro-3,7,1l-trimethyldodeca-2,4,l0- trienoate, which can be purified by chromatography.

Other aldehydes of formula V, such as the aldehydes of Example 8, are suitable starting materials for the process of this Example.

EXAMPLE The process of Example 2 is repeated using HF in place of HCl to prepare ethyl 4-fluoro-5-hydroxy- 3,7,1l-trimethyldodec-2-enoate and, similarly, ethyl 4-fluoro-5-hydroxy-l l-methoxy-3,7,l l-trimethyldodec-Z-enoate. Each of these fluorohydrins is converted into the respective S-mesylate and then used in the process of Example 4 to prepare ethyl 4-fluoro-3,7,lltrimethyldodeca-Z,4-dienoate and ethyl 4-fluoro-llmethoxy-3,7,l l-trimethyldodeca-2,4-dienoate, respectivcly.

EXAMPLE l6 2. A compound according to claim 1 wherein Z is hydrogen.

3. A compound according to claim 2 wherein each of R R and R is methyl.

4. A compound according to claim 3 wherein n is two and X is chloro.

5. A compound according to claim 4 wherein R is hydrogen and R is lower alkyl of one to four carbon atoms.

6. A compound according to claim 1 wherein Z is hydroxy or lower alkoxy of one to four carbon atoms.

7. A compound according to claim 6 wherein Z is lower alkoxy of one to four carbon atoms.

8. A compound according to claim 7 wherein Z is methoxy, ethoxy or isopropoxy.

9. A compound according to claim 8 wherein each of R R and R is methyl.

10. A compound according to claim 9 wherein n is two and X is chloro.

11. A compound according to claim 10 wherein R is hydrogen and R is lower alkyl of one to four carbon atoms.

12. A compound according to claim 1 wherein Z is chloro and n is two.

13. A compound according to claim 12 wherein each of R R and R is methyl; X is ChzlOlO; and R is lower alkyl of one to four carbon atoms- R R R CH 1 I R C-CH (CH CHCH HC=C -C CH- C OR n 2 I Z X wherein,

n is one or two;

X is bromo or chloro;

R is lower alkyl;

each of R R and R is methyl or ethyl;

R is hydrogen or methyl; and

Z is hydrogen, methyl, chloro. hydroxy or lower alkoxy of one to four carbon atoms.

14. A compound according to claim 13 wherein R is hydrogen.

15. The compound, ethyl 4-chlo ro-3,7,l l-trimethyldodeca-2,4-dienoate, according to claim 5.

16. The compound, isopropyl 4--chloro-l l-methoxy' 3,7,1 l-trimethyldodeca-2,4-dienoate, according to claim 11.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,862,969 Dated January 28, 1975 lnv fl Clive A. Henrick It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

[73] "Zolcon" should read Zoec0n Signed and Sealed this Twenty-sixth Of October 1976 [SEAL] Arrest:

RUTH C. MASON C: MARSHALL DANN 14119811718 ff Commissioner ofPatenIs and Trademarks 

2. A compound according to claim 1 wherein Z is hydrogen.
 3. A compound according to claim 2 wherein each of R2, R3 and R4 is methyl.
 4. A compound according to claim 3 wherein n is two and X is chloro.
 5. A compound according to claim 4 wherein R5 is hydrogen and R is lower alkyl of one to four carbon atoms.
 6. A compound according to claim 1 wherein Z is hydroxy or lower alkoxy of one to four carbon atoms.
 7. A compound according to claim 6 wherein Z is lower alkoxy of one to four carbon atoms.
 8. A compound according to claim 7 wherein Z is methoxy, ethoxy or isopropoxy.
 9. A compound according to claim 8 wherein each of R2, R3 and R4 is methyl.
 10. A compound according to claim 9 wherein n is two and X is chloro.
 11. A compound according to claim 10 wherein R5 is hydrogen and R is lower alkyl of one to four carbon atoms.
 12. A compound according to claim 1 wherein Z Is chloro and n is two.
 13. A compound according to claim 12 wherein each of R2, R3 and R4 is methyl; X is chloro; and R is lower alkyl of one to four carbon atoms.
 14. A compound according to claim 13 wherein R5 is hydrogen.
 15. The compound, ethyl 4-chloro-3,7,11-trimethyldodeca-2,4-dienoate, according to claim
 5. 16. The compound, isopropyl 4-chloro-11-methoxy-3,7,11-trimethyldodeca-2,4-dienoate, according to claim
 11. 